Alkyl phenols



Patented May 20, 1941 Roland Brltead, Kirkwood, Mo. assiznor to Sharp & Dohme, Incorporated, Philadelphia, Pa a corporation of Maryland Application October 10,1932, Serial No. 637,199 Renewed March 9, 1939 No Drawing.

18 Claims.

This application relates to alkyl phenols. It includes new methods of preparing these compounds and new products including both new alkyl phenols and antiseptic preparations containing alkyl phenols.

I have found it advantageous to prepare alkyl phenols by condensing an alcohol with a phenol in an acid solution. I find, for example, that alkyl phenols can be produced by condensing alcohols with phenols in a sulphuric acid solution. Moreover, I find that by condensing alco- Using zinc chloride asa condensing agent in a hydrochloric acid solution, there is a tendency for the phenol nucleus to attach itself to that carbon of the alcohol to which the greatest number of-other groups are already attached, thus normal butyl alcohol gives secondary butyl phenol and both isobutyl alcohol and tertiary hols with phenols in the presence of zinc chloride.

it is advantageous to employ an acid such as hydrochloric acid and that in the presence 0! this acid, a lower condensation temperature is required, for example, a temperature of about 120 to 135, a much smaller amount of zinc chloride is consumed and improved yields are obtained as compared with the condensation of alcohols with phenols in the presence of zinc chloride but not in acid solution. On condensing the zinc chloride in solutions of acids other than hydrochloric, hydrochloric acid is no doubt formed by reaction on the zinc chloride. The use of zinc chloride as a condensing agent in the presence of hydrochloric acid is of particular value in preparing secondary and tertiary alkyl phenols. By this process I find it possible to condense secondary amyl alcohol, which may contain pentanol-2 and pentanol-3, normal amyl alcohol, secondary butyl alcohol, secondary hexyl alcohol which may contain both hexanol-2 and hexanol-3, secondary heptyl alcohol, cyclo hexyl alcohol, tertiary amyl alcohol and tertiary butyl alcohol with phenol, cresols and guaiacol.

The invention includes as new products alkyl cresols, more particularly secondary amyl cresol, tertiary amyl cresol, secondary hexyl cresol, tertiary hexyl cresol and secondary butyl cresol, including alkyl ortho,.para and meta isomers and mixtures thereof; alsoalkyl guaiacols, more par- ,mers may be condensed with alcohols to give secondary hexyl ortho cresol, secondary hexyl meta cresol, secondary hexyl para cresol, secondary amyl meta cresol, and secondary butyl meta cresol, for example, all of which are new products and a part of this invention.

butyl alcohol give tertiary butyl phenol. Both pentanol-2 and pentanol-3 attach themselves to the ring in the ortho and para positions. Normal amyl alcohol gives a mixture containing both compounds in which the second and third carhorns are occupied. Iso-amyl alcohol and tertiary amyl alcohol both give tertiary amyl phenol. The secondary heptyl phenol boiling between 255 and 275 C. obtained by the condensation of phenol with normal heptyl alcohol is undoubtedly a mixture of the ortho and para isomers in which the ring is connected to one of the intermediate carbons in' the normal heptane chain. By distillation of the reaction mixtures, products are obtained, which are composed chiefly of the secondary alkyl phenols, although they may contian small amounts of other isomers, depending upon the purity of the starting materials and the reaction involved. For example, on condensing isopropyl alcohol with ortho cresol a mixture of compounds is obtained, the isopropyl group enalcohol or normal hexyl alcohol with a mixture of the cresols, accordingto my process, a still larger number of compounds is produced because the ring does not always attach to the same carbonof the paraifin chain, but according to my process the products are composed chiefly of secondary amyl and hexyl cresols, respectively.

I have found that by using an excess of normal butyl alcohol with a limited amount of concentrated hydrochloric acid normal butyl alcohol will condense smoothly with phenol in the presence of zinc chloride to give a product consisting of a mixture of butyl phenols containing more of the para-isomer than the ortho isomer, but consisting chiefly of other constituents than para,

secondary butyl phenol, such a product having a boiling range for example of from 220'250 C.,

and having a phenol coefllcient of around 37 I Without the use of hydrochloric acid, it has been customary in condensing alcohols with phenols using zinc chloride toheatthe reaction mixture to temperatures at or near the boiling point of the mixtures which is usually 160 C. or above. I have found that by using hydrochloric acid solutions for the condensations, the temperatures may be materially reduced. For example, in the condensation of normal butyl alcohol with phenol, a temperature around 130 to 135 C. may beemployed as compared with temperatures around 184 to 185 C. formerly employed for the condensation of these compounds without the use of an acid. The use of an excess of the alcohol, for

example, normal butyl alcohol above that which enters into reaction with the phenol increases the yield of the alkyl phenol product based upon the phenol employed.

The invention will be further illustrated by the following specific examples, the parts being by weight:

Example 1 s5 parts of phenol and l50'parts of zinc chloride are mixed and heated to 130-140 C. with vigorous agitation under a reflux condenser. To

oily reaction product is washed two or three times with water and is thus obtained as a crude reaction product. The excess alcohol and low boiling reaction products are removed by distillation until the temperature of the distillate reaches about 160 C.

For some purposes, as in the manufacture of certain antiseptic or disinfecting compositions, the crude reaction product can be employed without further purification, and without removal of any remaining phenol therefrom. This crude reaction product may contain some unchanged phenol and may also contain small amounts of tarry constituents. Its high phenol coeflicient makes it a valuable crude product for use where a refined or purified product is not required. Its high phenol coeflicient enables a small amount of it to be employed in place of much larger amounts, for example, of ordinary crude phenol.

The crude product can be further purified by subjecting it to distillation to remove first any unchanged phenol and then to distill the butyl phenol compositions over a boiling point range of, for example, from 220 C. up to around 255 o'r 265 C., leaving a tarry residue as the residue of the distillation. This product so obtained concaustic soda solution. The residue from the extraction with 5% caustic soda.solution appears to be made up to a considerable extent of higher 1 boiling phenols which appear as alkali insoluble constituents with 5% caustic soda solution but as alkali soluble constituents with 10% caustic soda solution. The entire distillate, however, boiling between around 220 and 255 or 265 C. can be advantageously employed without further refining or fractionation as a new butyl phenol composition which is free or substantially so from unchanged phenol and also free or substantially so from tarry impurities or constituents. The higher boiling and lower boiling constituents of this composite product, as well as the constituents of intermediate boiling point, form valuable ingredients of the new compositions, and the composition as a whole has a high phenol coeihcient, for example, around 35 to 40.

The product can be further purified by treating it with caustic soda solution to extract the butyl phenols and convert them into their sodium salts, where caustic soda is employed for the extraction, andthe resulting solution can be separated from undissolved constituents. Depending upon the strength of the caustic soda solution, a somewhat greater or smaller amount of phenols will be extracted. As pointed out above, a 10% caustic soda solution will extract phenols which will not be readily extracted with a 5% caustic soda solution. Such solutions of the sodium salts of the butyl phenols also form a valuable antiseptic or disinfecting composition and can be used as such-or as an ingredient of compositions intended for antiseptic or disinfecting purposes. By treating the solution of the sodium salts with an acid such as hydrochloric acid or carbon dioxide, the butyl phenols can be set free from the sodium salts and the composition again obtained in the form of an, oil which in this case will be free from alkali-insoluble constituents. It is not necessary to separate the alkali insoluble constituents for most purposes, but the composition containing such constituents can advantageously be employed. Such alkali-insoluble constituents if separated will be found to be relatively inert, although they may have a slight antiseptic action. The extracted phenols may be employed by themselves either in the form of their sodium salts, or in the form of the free phenols regenerated from the sodium salts. In such case, it is not necessary to further fractionate the oil to separate the higher and lower boiling constituents, but the composition as a whole can be advantageously employed, with its constituents boiling between 220 and 235 as well as its constituents boiling above 245 and up to tains various constituents of both lower, intermediate and higher boiling point. A large part of the compositions is soluble in dilute alkali using, for example 5% caustic soda solution. It is preferable to use an excess of the alkali solution, for example around in excess of that theoretically required. The residue remaining after such extraction with 5% caustic soda solution is to a considerable extent soluble in a stronger caustic soda solution, for example, a 10% The proportions of higher boiling, intermediate boiling and lower boiling constituents, will vary somewhat with the conditions of the condensing process. The yield will also vary somewhat with the process. I have obtained, for example, w'ithdiiferent processees, from around.

%, to nearly of the total distillate boiling between 220 and 235 C. I have obtained similar variations in the part of the distillate boiling between 245 and 265 C. The portion of the oil distilling between 235 and 245 C. has varied from considerably less than half the total 011 up to more than half. I The fraction boiling between 235 and 245 C. undoubtedly contains considerable amounts of para-secondary butyl phenol, but it also contains considerable amounts of other phenols including ortho-secondary.butyl phenol in substantial amounts, although the ortho-secondary butyl phenol will be largely I to separate them from each other by fractional distillation. Thereis no need, however, of so separating them because they can advantageously' be employed in admixture, and without separation, as a composite product having a high phenol coefilcient. For example, the fraction boiling over the range oi 235 to 250 C. has a phenol coemcient of about 38, while the total oil containing both higher and lower boiling constituents has a phenol coefficient approximately the same, varying, for example, from around 35 or somewhat lower to 40 or somewhat higher. By the use of proper apparatus and repeated distillations and crystallizations the para-secondary butyl phenol of boiling point of 240-242 C. and melting point 60-62" C. can be obtained, and also the ortho-secondary butyl phenol of boiling point 227 to 229 C.; but as abovepointed out, there is no need ,of. separating these indi-' vidual phenols, or fractions consisting chiefly of them, bwause the composite product constitutes. a valuable product of high phenol coefficient in much larger yields than would be the yield of the individual butyl phenols.

Ordinarily, where the crude product without further refining is not to be employed, a distillation oi the crude product to remove unchanged phenol and tarry residue will be all that is needed; or the crude product can be subjected to alkali extraction, either before or after distillation, to separate the alkali-insoluble constituents from the alkali-soluble constituents, and these separated constituents can be employed separately for use as antiseptic or disinfecting compositions. When the crude product is purified by dissolving the butyl phenols in caustic alkali, separating the solution from the undissolvedi residue and acidifying the solution to set free the butyl phenol composition as an oil, this oil may be employed without further distillation, or it can then be distilled in case, for example, it

still contains small amounts of unchanged phenol or of tarry residue which can be removed by distillation, giving a distillate boiling, for example, between 220 and 255 C. or 265 C.

' Example 2 Example 3 62 parts of guaiacol and 45 parts of zinc chloride are heated together until solution occurs. 10 parts of concentrated hydrochloric acid in 46 parts of tertiary hexyl alcohol (Dimethyl-npropyl carbinol) are added in several portions while the temperature isheld at l-130 C. The resulting oil is purified by dissolving .in twice its volume of benzene and ,extracting with several portions of dilute sodi hydroxide. The alkaline extracts are com ined, acidified and! the recovered phenolic material distilled. The product which distills over between 275 and 290 C. is collected as tertiary hexyl guaiacol. It is a new product.

' Example 4 420'parts of phenol and 200 parts of zinc chloride are heated together until solution is almost complete. A solution of 40 parts of concentrated hydrochloric acid in 400 parts of cyclohexanol are added in portions while the temperature is held at 100-130 C. The resulting oil is washed and distilled. The portion boiling from 250 to 300 C. is largely p-cyclohexyl phenol which can be crystallized from benzene or toluene. The

, corresponding ortho isomer can be obtainedby fractionation of. the mother liquor from the para isomer.

Example 5 225 parts of phenol and 200 parts of zinc chloride are heated until solution is nearly complete.

. A solution of 50 parts of concentrated hydrochloric acid in 225 parts of secondary butyl alcohol is added in-portions while the temperature is held at IOU-140 C. The oil is washed with water and distilled. This product with a boiling point of about, 220-255 C. contains a small amount of non-phenolic material from which it may be freed by extraction of its alkaline solution with a suitable solvent.

' Example 6 40 parts of phenol are mixed. with parts of After one hour, nine parts more of acid are added slowly and the heating continued for three hours. The oil is washed with water and distilled; The tertiary amyl phenol which distills over may be purified by crystallization from a suitable solvent.

Example 7 3000 parts of cresol was heated with stirring to 130 when 2500 grams of zinc chloride was added slowly. A solution of 350 parts of concentrated hydrochloric acid in 2500 parts of secondary hexyl alcohol was added during three Example 8 5'70 parts of U. S. P. Cresol and 1000 parts 01. zinc chloride are heated to 120 C. with stirring. A mixture of 165 parts of concentrated: hydrochloric acid and 825 parts of n-butyl alcohol areadded during two hours while the mixture is held at -135 C. During the next three hours a mixture of 600 parts of n-butyl alcohol and 85 parts of concentrated hydrochloric acid are added. The lower aqueous layer is separated'and the oil washed with water. The oil is then distilled. The product distilling between 240 and 263 C. is collected as secondary butyl cresol. It is a new product.

Example 9 500 parts of U. S. P. Cresol and 500 parts of zinc chloride are heated with stirring to, C. 475 parts of secondary butyl alcohol containing 70 parts of concentratedhydrochloric acidis added during two hours while the temperature is maintained at 115-130 C. The lower aqueous 1 layer is then separated; the oil washed with water and distilled, the product distilling between 235-265" C., being collected as secondary butyl cresol. It is a new product. I Example 500 parts of meta cresol and 500 parts of zinc chloride are heated with stirring to 120 C. 475 parts of secondary butyl alcohol containing 70 parts of concentrated hydrochloric acid is added during two hours while the temperature is maintained at 115-130 C. The lower aqueous layer is then separated; the oil washed with water and distilled, the product distilling between 241 and 255 C., being collected as secondary butyl meta cresol. It is a new product.

Example 11 365 parts of meta cresol is mixed with 340 parts of zinc chloride and heated to 130 C. 330 parts of mixed secondary amyl alcohols, containing 65 parts of concentrated hydrochloric acid, is added during two hours while the temperature is maintained at 120-130 C. The temperature is held at 130 C. for two hours longer; after which the lower aqueouslayer is removed and the oil washed with water. The product is distilled and the fraction coming over 'between 245-260 C., collected as secondary amyl meta cresol. Itis a new product.

Example 12- 365 parts of U. S. P. Cresol is mixed with 340 parts of zinc chloride and heated to 130 C. 330 parts of mixed secondary amyl alcohols, containing 72 parts of concentrated hydrochloric acid, is added during two hours while the temperature is maintained at 120-130 C. The temperature is held at 130 C. for two hours longer, after which the lower aqueous layer is removed and the oil washed with water. The product is distilled and the fraction coming over between 245-270 C.

ed hydrochloric acid, is added during three hours while the temperature is maintained at 120 to 135 C. After one hour longer heating and stirring, the lower aqueous layer is removed andthe oil washed with water. The product is then distilled andthat portion coming over between 250 and 300 C., or on distillation at 8 mm. that portion coming over at Mil-160 C. is collected as secondary hexyl cresol.. It is a new product.

Example 16 300 parts of meta cresolis mixed with 300 parts of zinc chloride and heated to 125 C. 310 parts of secondary hexyl alcohol containing 50 parts of concentrated hydrochloric acid is added during two hours. The temperature is maintained at 120-130 C. one hour longer while the mixture is stirred. The lower aqueous layer is then removed and the oil washed with water. The prodnot is then distilled and that portion distilling between 260 and 290 or 300 C. is collected as secondary hexyl meta cresol. It is a new product.

Erample 17 300 parts of ortho cresol is mixed with 300 parts of zinc chloride and heated to 125 C. 310 parts 01' secondary hexyl alcohol containing 50 parts of concentrated hydrochloric acid is added collected as secondary amyl cresol. It i'sa new product.

Example 13 337 parts of phenol and 337 parts of zinc chloride are mixed and heated with stirring to 125 C. 337 parts of mixed secondary amyl alcohols containing 68 parts of concentrated hydrochloric acid is added during five hours while the temperature is kept between 120 and- 135 C. After heating one hour longer, the lower aqueous layer is removed and the oil washed with water. The

oil is then distilled, the fraction coming over between 232 or 240 and 260 0., being collected as secondary dmyl phenol. It is a new product.

Example 14 3000 parts of U. S. P. Cresol is mixed with 2800 parts of zinc chloride. 3500 parts of secondary hexyl alcohol, containing 500 parts of concentratduring two hours. The temperature is maintained at -130 C. one hour longer while the mixture is stirred. The lower aqueous layer is then removed and. the oil washed with water. The product is then distilled and that portion dis tilling between-250470 or 275 C. is collected as secondary hexyl ortho cresol. It is a new product. Example 18 300 parts of para cresol is mixed with 300 parts of zinc chloride and heated to C. 310 parts of secondary hexyl alcohol containing 50 parts of concentrated hydrochloric acid is added dur ing two hours. The temperature is maintained at 120-130 C. one hour longer while the mixture is stirred. The lower aqeous layer is then removed and the oil washed with water. The product is then distilled and that portion distilline between 265 and 290 or 300 C. is collected as secondary hezwl para cresol. It is a new prod uct.

Example 19 I 500 parts of U. S. P. Cresol is mixed with 325 partsof zinc chloride and heated to 120-130 C. 500 parts of tertiary amyl alcohol containing 100 parts of concentrated hydrochloric acid is added during two hours while the temperature is held at 100-130 C. or as near 100 as refluxing permits. The mixture is then heated one hour longer with stirring. then removed; the oil washed with water. The product is distilled and'fraction coming over be. tween 240 and 260 or 265 C. and collected as tertiary amyl cresol. It is a new product.

It is understood, or course, that the relative amounts of each ingredient used in the examples above may be varied over considerable limits, aflecting only the yield.

The amyl and hexyl alcohols used were mixtures of the secondary alcohols available commercially. The use of any individual alcohol isomer would result in the'production of the same mixture of phenols, diflering only in the relative amounts of each phenolic isomer. U. S. P. Cresol has been used as a typical commercially available mixture of the three cresols. Since this mixture may vary over wide limits in regard to the rela- The lower aqueous layer is uct obtained from such a mixture of cresols will contain varying amounts of the derivatives of the isomeric cresols somewhat in proportion to the amounts of each isomer present in the mixed cresols used.

The use of n-amyl or n-hexyl alcohol in place of the secondary alcohols would also lead to products differing but slightly, if at all, from those obtained from secondary alcohols.

The compound prepared as dmcribed in Example 1 is claimed as a new product in my copending application, Serial No. 258,151, filed February 29, 1928, now matured into Patent No. 1,887,662, issued Nov. 15, 1932,'of which this application is in part a continuation.

The reaction employing zinc chloride as a condensing agent in the presence of an acid may be applied generally to the condensation of alcohols with phenols. In this manner, the following new compounds have been prepared:

Secondary heptyl phenol boiling around 255-2'75 Te tlary hexyl cresol boiling around 250-260 0.; Secondary butyl guaiacol boiling around 245270 SeSondary amyl guaiacol boiling around 250-268 se ondary hexyl guaiacol boiling around 255-275 Cy clo 122m guaiacol boiling around 300-308" C.

- containing phenol-or cresol which already have antiseptic properties, for example, the addition of from 1% to of an alkyl phenol such as a mixture of secondary hexyl cresols, for example, to a solution containing 35% of soap and 50% of a mixture of cresols and 5% of water and glycerin will give an antiseptic solution very much more active than the same solution without the addition of the alkyl phenol. Also a solution containing about 7% of soap, 6% of a mixture of cresols and 6% of a mixture of secondary hexyl cresols or other alkyl phenols, the balance being water is an antiseptic and may be used full strength or diluted with large amounts of water, 5 as desired. In antiseptic soap solutions of this type, I prefer to use a linseed oil soap solution,

although cocoanut oil or other fatty oils may be 'used as a basis for the soap instead of linseed oil, if desired. The amounts of cresol used may 6 vary over wide limits. A mixture of the cresol isomers and the hexyl cresol isomers or a single cresol and hexyl cresol isomer may be employed. The resulting solutions upon dilution give more or less permanent emulsions depending upon the relative amounts of each ingredient present. Small amounts of other solvents may be added such as alcohol, acetone, ethylene glycol or an ethylene glycol ether, or diethylene glycol or a diethylene glycol ether.

Certain of the alkyl phenols may be taken internally and may be employed as urinary antiseptics. The efiect of such antiseptics depends somewhat upon the diet of the animal under consideration. They may be administered as 7 an oil solution inclosed in a gelatin capsule. A

' mixture of the secondary hexyl cresols exerts an anthelmintic action in addition to its antiseptic action and is to be recommended for treatment of the intestinal and urinary tracts. In general, the higher members of any series of alkyl phenols are less toxic and less escharotic than the lower. The secondary hexyl cresols and phenols, secondary amyl cresols and phenols and secondary butyl cresols and phenols are markedly antiseptic. and relatively non-toxic. The secondary hexyl, amyl and butyl cresols have no appreciable escharotic action. They may be incorporated in oils such as olive or cottonseed oil for this purpose and if desired, such solutions may be administered in elastic gelatin capsules.

Most of the alkyl phenols are relatively insoluble in water but all may be dissolved in alcohol or alcohol and water with or without the addition of other diluents such as glycol, glycerin, etc. and such deodorant solutions may be employed as oral antiseptics or general antiseptics. For example, a 30% alcohol solution containing, for example, about one part in 1000 of these alkyl phenols has marked antiseptic properties. Moreover, a mixture of two or more phenols usually has a greater activity than would be expected for the activity of each individual. For this reason, the alkyl phenols are useful additions to other phenolic germicides incorporated in such solvents as those last mentioned. As an example, tertiary amyl phenol added to a solution of another phenol, for example'phenol in one of the solvents mentioned above gives a solution more active than would be anticipated from the actionoi' tertiary amyl phenol or phenol alone.

The alkyl phenols may be incorporated into jellies and ointments which alsoinclude a solvent for both phenol and water, for example jellies prepared from such materials as tragacanth, acacia, etc. and containing glycerin, alcohol, ethylene glycol or like solvents may be given antiseptic properties by the incorporation of small amounts of alkyl phenols. For example,'a semifiuid jelly prepared from tragacanth and acacia containing from 10 to 25% glycerin and from about 1 to 500 to 1 to 2000 parts, more or less, of secondary hexyl cresol or secondary amyl phenol has antiseptic properties.

The alkyl phenols may be incorporated in petrolatum base ointments, particularly if a second ingredient soluble in both oils and water such as dioxan, lanolin and the ethers of ethylene and diethylene, glycol is added for the purpose of assisting the extraction of the phenol from the ointment base by surrounding aqueous fluids The alkyl phenols which. are comparatively non-toxic are strongly antiseptic and may ad-'- vantageously be used in small amounts for the preservation of cosmetics, powders, jellies and food products in general, particularly those not. containing large amounts of nitrogenous materials.

I claim:

1. The method of producing alkyl phenols which comprises condensing a monohydric alcohol and a phenol in an acid solution of a condensing agent.

2. A method 'ofproducing alkyl phenols which comprises subjecting a monohydric alcohol and a phenol to condensation in the presence of zinc chloride in a hydrochloric acid solution.

ride with the addition concentrated hydrochloric acid. a

4. The method of producing butyl phenol compositions which comprises subjecting normal butyl alcohol and phenol to condensation with zinc chloride and hydrochloric acid at a temperature around 130 to around 135 C.

5. The method of producing butyl phenol compositions which comprises subjecting butyl alco-' hols and phenols to condensation with zinc chloride and hydrochloric acid, the butyl alcohols being employed in excess.

6. The method of producing alkyl phenols which comprises subjecting a. monohydric ,alcohol and a phenol to condensation with zinc chloing a monohydric alcohol containing ,at least three carbon atoms in a straight chain and, a phenol to condensation with zinc chloride in the presence of an acid.

9. The method of producing alkyl phenols which comprises subjecting a monohydric alcohol 30 and phenol to condensation in the presence of zinc chloride and hydrochloric acid.

10. A method of producing alkyl phenols which comprises subjecting a monohydric alcohol and a cresol to condensation in the presence of 35 zinc chloride and hydrochloric acid.

11. The method of producing alkyl phenols which comprises subjecting a monohydric alcohol and guaiacol to condensation in the presence 40 of zinc chloride and hydrochloric acid.

12. A process for. the production of tertiary alkyl phenols which comprises'condensing a tertiary alcohol and a phenol in an acid solution of a condensing agent.

13. A process ior the production of tertiary 45 alkyl phenols which comprises condensing a tertiary-alcohol and a phenol in the presence of zinc chloride and an acid.

14. Secondary alkyl phenols having the following !ormula:

10 having 6 carbon atoms in the alkyl radicals, and

having valuable therapeutic properties as an antiseptic and germicide; R and R representing alkyl radicals. v

15. Composition of matter composed mainly oi. a. hydroxylated aromatic nucleus with a carbon atom attached directly thereto and which is also directly attached to two other carbon atoms, forming a secondary alkyl group containing more than 4 but less than 7 carbon atoms.

16. Secondary amyl phenols, havingthe following formula:

being colorless liquids boiling at 232 to 260 C.,

and being a valuable therapeutic agent as an antiseptic and germicide.

17. Secondary hexylphenols having the following formula:

CsHi3(CsH4) OH being colorless liquids boiling at 250 to 275 C., and being a valuable therapeutic agent as an antiseptic and germicide.

18. As new compounds, secondary alkyl phenols having the formula in which R is a secondary alkyl group having from flve to seven carbon atoms.

ROLAND R. READ. 

